Iron(III)-Catalyzed Ortho-Preferred Radical Nucleophilic Alkylation of Electron-Deficient Arenes

The untraditional iron-catalyzed, ortho-preferred, radical alkylation of electron-deficient (hetero)arenes is reported. A variety of electron-deficient arenes were shown to react with various primary alkyl sources, producing the alkylated (hetero)arenes in good yields. This reaction might be an alkyl radical, nucleophilic aromatic substitution reaction, rather than the traditional electrophilic Friedel-Crafts reaction. HOMO-LUMO analysis and DFT studies on the key transition states underlying the regioselectivity are consistent with the observed reactions and the conclusions.